Antioxidant aromatic fluorophosphites

ABSTRACT

Organic materials normally subject to gradual degradation in the presence of oxygen are stabilized by inclusion of an aromatic fluorophosphite having at least one benzene group bonded through oxygen to phosphorus and at least one fluorine atom bonded directly to the same phosphorus. Stabilization is improved by also including a conventional phenolic antioxidant. Many of the aromatic fluorophosphites are new compounds.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to aromatic fluorophosphorus compounds and theiruse as antioxidants in organic materials such as organic polymers.

2. Description of the Prior Art

Phosphites, phosphonites and other organic phosphorus compounds are usedin organic polymers and other organic materials as antioxidants. Theyare generally considered better than phenolic antioxidants at hightemperatures because they eliminate hydroperoxides which decompose andlead to autooxidation chain reactions. Thus, phosphorus compounds areimportant for oxidative stability during various operations includingpolyolefin extrusion.

Phenolic and phosphorus antioxidants are often used together inpolyolefin homopolymers and copolymers to provide antioxidant protectionfor both low and high temperature exposure. Unfortunately, additionalexpense is encountered as additives in larger amounts are needed for thepolymers. Thus, there exists a need for effective antioxidants at areasonable additive price, not only for polyolefins, but othersubstrates as well.

It is common practice to include an antioxidant in organic materialsnormally susceptible to oxidative degradation. Many of the antioxidantsemployed have limited effectiveness or tend to impart undesirableproperties to the organic material such as causing color. The problem isparticularly acute with polymers and copolymers of ethylenicallyunsaturated monomers, especially polyolefins such as polypropylene. Thematerials are subjected to elevated temperatures during processing,which tends to destroy many antioxidants with the result that thepolymer rapidly degenerates during use. The aromatic fluorophosphoruscompounds of the present invention allow organic materials to maintainexcellent color and thermal stability.

SUMMARY OF THE INVENTION

According to the present invention, certain aromatic fluorophosphoruscompounds are provided which are very effective as stabilizers in a widerange of organic materials. The aromatic fluorophosphorus compounds arevery effective because they retard changes in viscosity of organicmaterials stabilized therewith for extensive periods of time underprocessing conditions. In addition, they are stable when stored at roomtemperatures. They are especially effective when used in combinationwith phenolic antioxidants.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

A preferred embodiment of the present invention is an organic materialnormally susceptible to gradual oxidative degradation when in contactwith oxygen said organic material containing an antioxidant amount of anaromatic fluorophosphorus compound being characterized by having atleast one benzene group bonded through oxygen to a trivalent phosphorusatom and at . .leas.!. .Iadd.least .Iaddend.one fluorine atom bonded tothe same phosphorus atom.

Any organo phosphorus compound meeting the above definition is readilyrecognize by its structural formula. One highly preferred class of suchcompounds can be represented by the formula:

    (RO--).sub.n P(--F).sub.3--n                               Formula I

wherein R is a . .substitute.!. .Iadd.substituted .Iaddend.orunsubstituted aryl group wherein the substituents are selected fromalkyl, aryl, aralkyl, cycloalkyl, hydroxy, alkoxy, aryloxy, halo,alkoxycarbonyl, alkoxycarbonylalkyl an acyloxy and n is 1 or 2. In astill more preferred embodiment of this class of compounds thesubstituents are alkyls having . .1-carbon.!. .Iadd.1-20 carbon.Iaddend.atoms, aryls having 6-12 carbon atoms, arylalkyls having 7-12carbon atoms, cycloalkyls having 5-8 carbon atoms, hydroxy, alkoxyhaving 1-12 carbon atoms, aryloxy having 6-12 carbon atoms, halo,alkoxycarbonylalkyl having 1-20 carbon atoms in its alkoxy moiety and1-3 carbon atoms in its alkyl moiety, alkoxy carbonyl having 1-20 carbonatoms in its alkoxy moiety and acyloxy having 1-4 carbon atoms.

Representative examples of the above substitutents are methyl,isopropyl, sec-butyl, tert-butyl, n-decyl, sec-dodecyl, sec-eicosyl,phenyl, o-tolyl, p-tolyl, naphthyl, 4-phenylphenyl, 4-sec-hexylphenyl,benzyl, alphamethylbenzyl, phenethyl, 4-tert-butylbenzyl,4-tert-butyl-alphamethylbenzyl, cyclopentyl, cyclohexyl, cyclooctyl,methoxy, ethoxy, isopropoxy, 2-ethylhexoxy, 2-ethoxyethoxy, isobutoxy,dodecoxy, phenoxy, 4-ethylphenoxy, napthoxy, 4-phenylphenoxy, chloro,bromo, fluoro, iodo, methoxycarbonylmethyl, butoxycarbonylethyl,dodecyloxycarbonylpropyl, octadecyloxycarbonylethyl,icosyloxycarbonylethyl, methoxycarbonyl, butoxycarbonyl,decyloxycarbonyl, octadecyloxycarbonyl, icosyloxycarbonyl, formate,acetyloxy, propionyloxy, butyryloxy and the like.

Representative examples of the group (RO) include phenoxy,2-methyl-6-tert-butylphenoxy, 2,4-di-tert-butylphenoxy,2,6-diisopropylphenoxy, 2,4-diisopropllphenoxy, 2,6-di-sebutylphenoxy,4-phenylphenoxy, 2-(alpha-methylbenzyl)phenoxy2,6-di(alpha-methylbenzyl)phenoxy, 2-cyclohexylphenoxy,2-methyl-4-cyclohexylphenoxy, 4-hydroxyphenoxy, 4-methoxyphenoxy,2-ethoxyphenoxy, 4-dodecyloxyphenoxy,4-phenoxyphenoxy,4-octadecyloxycarbonylethyl-2,6-di-tert-butylphenoxy,-dodecyloxycarbonylpropyl, 4-acetyloxyphenoxy and the like.

Some representative compounds of Formula I are: bis(2,6-di-tert-butylphenyl) fluorophosphite; 2,6-di-tert-butylphenyldifluorophosphite; bis(2,4-di-tert-butylphenyl) fluorophosphite;2,4-di-tert-butylphenyl difluorophosphite;bis(4-(2-octadecyloxycarbonylethyl)-2,6-di-tert-butylphenyl)fluorophosphite;

(aka bis2,6-di-tert-butyl-4-(2-carbooctadecyloxyethyl)phenyl!fluorophosphite);4-(2-octadecyloxycarbonylethyl)-2,6-di-tertbutylphenyldifluorophosphite;bis(4-(2-dodecyloxycarbonylethyl)-2,6-di-sec-butylphenyl)fluorophosphite and the like.

The most preferred compounds in Formula I are:bis(2,6-di-tert-butylphenyl) fluorophosphite:bis(2,4-di-tert-butylphenyl) fluorophosphite andbis(4-(2-octadecyloxycarbonylethyl)-2,6-di-tert-butylphenyl)fluorophosphite.

A second highly preferred class of compounds of the invention are thecyclic fluorophosphites having the structure ##STR1## wherein R¹ and R²are substituted or unsubstituted aryl groups wherein the substituentsare selected from alkyl, aryl, aralkyl, cycloalkyl, hydroxy, alkoxy,aryloxy and halo, and X is selected from the group consisting of asingle bond connecting R¹ and R² and divalent bridging groups selectedfrom divalent aliphatic hydrocarbons containing 1-12 carbon atoms, --0--and --S_(q) wherein q is an integer from 1 to 3.

In a still more preferred embodiment of the cyclic fluorophosphite ofFormula II, the substituent groups on R¹ and R² are alkyls having 1-20carbon atoms, aryls having 6-12 carbon atoms, aralkyls having 7-12carbon atoms, cycloalkyls having 5-8 carbon atoms, hydroxy, alkoxyhaving 1-12 carbon atoms, aryloxy having 6-12 carbon atoms and halo, andX is selected from the group consisting of a single bond connecting R¹and R² and divalent bridging groups selected from divalent aliphatichydrocarbons containing 1-12 carbon atoms, --0-- and --S_(q) wherein qis an integer from 1 to 3. Examples of the resulting --R¹ --X--R² --groups are 2,2'-bis(4,6-di-tert-butylphenyl);2,2'-bis(4-chloro-6-isopropylphenyl):2,2'-bis(4-methoxy-6-tert-pentylphenyl);2,2'-methylenebis(4,6-di-tert-butylphenyl);2,2'-ethylidenebis(4,6-di-tert-butylphenyl);4,6,-di-tertbutyl-4,-methyl-6-isopropyl-2,2'-isopropylidenebisphenyl;2,2'thiobis(4-methyl-6-tert-butylphenyl);2,2'-trithiobis(4,6-di-tert-butylphenyl);2,2'-thiobis(4-methoxy-6-tert-butylphenyl);2,2'-dithiobis(4-methyl-6(alphamethylbenzyl)phenyl).

A third highly preferred embodiment is represented by the structure:##STR2## wherein R is a substituted or unsubstituted aryl group whereinthe substituents are selected from alkyl, aryl, aralkyl, cycloalkyl,hydroxy, alkoxy, aryloxy, halo, alkoxycarbonyl, alkoxycarbonylalkyl andacyloxy and R³ is selected from the group consisting of alkyl,cycloalkyl, aralkyl, aryl, substituted aryl, alkoxy, cycloalkoxy,aryloxy and aralkoxy radicals.

The preferred R of substituents are alkyls having 1-20 carbon atoms,cycloalkyls have 5-8 carbon atoms, aryls having 6-12 carbon atoms,aralkyls having 7-12 carbon atoms, hydroxy, alkoxy having 1-12 carbonatoms, aryloxy having 6-12 carbon atoms, halo, alkoxycarbonylalkylhaving 1-20 carbon atoms on its alkoxy moiety and 1-3 carbon atoms onits alkyl moiety, alkoxycarbonyl having 1-20 carbon atoms in its alkoxymoiety and cyloxys having 1-4 carbon atoms. R³ . .s.!. .Iadd.is.Iaddend.more preferably selected from alkyls having 1-20 carbon atoms,cycloalkyls having 5-8 carbon atoms and arylalkyls having 7-12 carbonatoms which are bonded through oxygen to phosphorus and aryls having6-12 carbon atoms, alkyls having 1-20 carbon atoms, cycloalkyls having5-8 carbon atoms and arylalkyls having 7-12 carbon atoms which arebonded directly to phosphorus.

Representative examples of R---O -- in formula III are the same setforth for this same group under structure I.

Representative examples of R³ in formula III are methoxy, sec-butoxy,decoxy, 2-ethyldecoxy, octadecoxy, eicosoxy, cyclopentoxy, cyclohexoxy,cyclooctoxy, phenoxy, 2,6-di-tertbutylphenoxy, 2,4-di-tert-butylphenoxy,2-tert-butyl-4methylphenoxy, 4-methoxyphenoxy, benzyloxy,4-ethylbenzyloxy, phenyl, p-tolyl, 4-phenylphenyl, methy, ethyl, butyl,dodecyl, octadecyl, eicosyl, cyclohexyl, cyclooctyl, benzyl,4-ethyl-alpha-methylbenzyl and the like.

Typical compounds of structure III are methyl phenyl fluorophosphite,dodecyl 2,6-di-tert-butylphenyl fluorophosphite, eicosyl2,4-di-tert-butylphenyl fluorophosphite, cyclohexyl2,6-di-tert-butyl-4-ethoxyphenyl fluorophosphite, diphenylfluorophosphite, bis(2,6-di-tert-butylphenyl) fluorophosphite,bis(2,4-di-tert-butylphenyl) fluorophosphite,bis(2,4-di-tert-pentylphenyl) fluorophosphite, benzyl2(alpha-methylbenzyl)-4-chlorophenyl fluorophosphite, phenyl2-methyl-6-tert-butyl-4-phenoxyphenyl fluorophosphite,2,4-di-tert-butylphenyl methylfluorophosphonite,2,6-di-tert-butyl-4-methylphenyl benzylfluorophosphonite,2,6-di-tert-butyl-4-methoxyphenyl eicosylfluorophosphonite and the like.

A fourth class of fluorophosphorus compounds of the invention arerepresented by the structure: ##STR3## wherein A is a mono- orpoly-nuclear aromatic group, R⁴ is independently selected from fluorine,aryloxy, alkaryloxy, alkoxy and polyalkoxy and r is an integer from 1 to4, s is an integer from 0 to 3 and (r+s) equals the valence of A.

Representative examples of R⁴ in formula IV are fluorine, phenoxy,4-ethylphenoxy, 2-ethyl-4-isobutylphenoxy, napthoxy,2-tert-butylphenoxy, 2,6-di-tert-butylphenoxy,2-methyl-6-tert-butylphenoxy, 2,4-di-tert-butylphenoxy,2,6-di-sec-butylphenoxy, 2,6-di-tert-butyl-4-methylphenoxy,4-dodecylphenoxy, 4-(alphamethylbenzyl)phenoxy, methoxy, ethoxy, butoxy,decyloxy, dodecyloxy, eicosyloxy, 2-ethoxyethoxy, 2butoxyethoxy and thelike.

"A" in Formula IV can be any of a broad range of organo groups as longas it contains at least one benzene ring in its structure "A" cancontain 4 or more benzene rings. "A" is generally but not necessarily ahydrocarbon. "A" may also contain oxygen and/or nitrogen.

The group "A" of the more important types of structure for compounds IVfall in the following sub-classes.

Sub-class IV (i) A groups have the structure: ##STR4## wherein R⁵ and R⁶are hydrogen or alkyls having 1-12 carbon atoms. Representative examplesof these divalent phenylene groups are 1,4-phenylene, 1,2-phenylene,2,6-di-tert-butyl-1,4-phenylene, 2,5-di-tert-butyl-1,4-phenylene,2-methyl-5-dodecyl-1, 4-phenylene and the like.

Representative examples of fluorophosphorus compounds containing the "A"group IV (i) are 2,5-di-tert-butyl-1,4-phenylene bis(difluorophosphite);2,5-tert-butyl-1,4-phenylene bis(phenyl fluorophosphite);3,5-di-tert-butyl-4-hydroxyphenyl difluorophosphite;2,5-di-tert-butyl-4-hydroxyphenyl octadecyl fluorophosphite;2,4-di-tert-butylphenyl 2-(alpha-methylbenzyl)-4-hydroxyphenylfluorophosphite; 2,6-di-tert-butylphenyl2-methyl-4-hydroxy-5-tert-butylphenyl fluorophosphite;2-dodecyl-4-hydroxy-5-methylphenyl dodecyl fluorophosphite;2,5-di-tert-butyl-1,4-phenylene bis(2,6-di-tert-butylphenylfluorophosphite) and the like.

Sub-class IV (ii) A groups have the structure: ##STR5## wherein R⁵ andR⁶ are as before, R⁹ is an aliphatic hydrocarbon radical having 1 to 6carbon atoms and having valence y and y is an integer from 2 to 3.

Representative compounds of sub-class IV (ii) are:¹ "T" represents atert-butyl group ##STR6##

Sub-class IV (iii) A groups have the structure: ##STR7## wherein R⁵ andR⁶ are as before and x is an integer from 1 to 3. Representativeexamples of structure IV (iii) A groups are:4,4'-thiobis(2-methyl-6-tert-butylphenyl),4,4'-thiobis(2,6-di-tert-butylphenyl),4,4'-dithiobis(2,6-di-tert-butylphenyl), . .22.!..Iadd.2,2'.Iaddend.,-dithiobis(4-methyl-6-tert-butylphenyl),2,2'thiobis(4-tert-butylphenyl) and the like.

Representative examples of organo fluorophosphorus compounds of formulaIV containing sub-class IV (iii) A groups are:4,4'thiobis(2-methyl-6-tert-butylphenyl diflurophosphite),4,4'-thiobis(2-ethyl-6-tert-butylphenyl butyl fluorophosphite),4,4'-thiobis(2,6-di-tert-butylphenyl difluorophosphite),4,4'-dithiobis(2,6-di-tert-pentylphenyl phenyl fluorophosphite) and thelike.

Sub-class IV (iv) A groups have the structure: ##STR8## wherein R⁵ andR⁶ are as before. Examples of these biphenyl groups are ##STR9##Representative examples of formula IV organo fluorophosphorus compoundsof sub-class IV (iv) are: ##STR10##

Sub-class IV (v) A groups have the structure: ##STR11## wherein R⁵ andR⁶ are as before, R⁷ is hydrogen or an alkyl having 1-6 carbon atoms, tis an integer from 2 to 3, u is an integer from 0 to 4 and (t+u) equals2 to 6.

Representative examples of organo fluorophosphorus compounds of FormulaIV having a sub-class IV (v) A group are: tris(difluorophosphite ester)of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; tris(phenyl fluorophosphiteester) of 1,3,5-trimethyl-2,4,6-tris 3,5di-tert-butyl-4-hydroxybenzyl!benzene; tris(n-dodecyl fluorophosphiteester) of 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)benzene; bis (2-tert-butylphenylfluorophosphite ester) of 2,3,5,6-tetramethyl-1,4-bis-3,5-di-tert-butyl-4-hydroxybenzyl!benzene; bis(n-octyl fluorophosphiteester) of 2,3,5,6-tetraethyl1,4-bis(3,5-ditert-butyl-4-hydroxybenzyl)benzene;tris(2,6-di-tert-butyl-4-methylphenyl fluorophosphite ester) of1,3,5-tris(3-methyl-5-tert-butyl-4-hydroxybenzyl!benzene;bis(2,6-di-tertbutylphenyl fluorophosphite ester) of 1,4-bis3,5-di-tert-butyl-4hydroxybenzyl!benzene;tris(2,6-di-tert-butyl-4-ethylphenyl fluorophosphite ester) of2,4,6-triethyl-1,3,5-tris 2-methyl-6-tert-butyl-4-hydroxybenzyl!benzeneand the like.

Sub-class IV (vi) A groups have the structure: ##STR12## wherein R⁵ andR⁶ are as before, R⁸ is an aliphatic hydrocarbon radical having 1-30carbon atoms and having valence w, w is an integer from 1 to 4 and v isan integer from 0 to 4.

Representative examples of organo fluorophosphorus compounds of FormulaIV having sub-class IV (vi) A groups are:2-methyl-6-tert-butyl-4(methoxycarbonylmethyl)phenyl difluorophosphite;2,6-di-tert-butyl-4(dodecyloxycarbonyl)phenyl2,6-di-tert-butyl-4-methylphenyl fluorophosphite;2,6-i-tert-butyl-4-(octadecyloxycarbonylethyl)phenyl difluorophosphite;2,6-di-tert-butyl-4-(octadecyloxycarbonylethyl)phenyl2,4-di-tert-butylphenyl fluorophosphite;2,6-di-tert-butyl-4-(octadecyloxycarbonylethyl)phenyl n-decylfluorophosphite; 2,6-di-tert-butyl-4-(octadecyloxycarbonylethyl)phenyl2,6-di-tert-butylphenyl fluorophosphite;2,6-di-tert-pentyl-4-(octadecyloxycarbonylethyl) phenyl2-tert-pentylphenyl fluorophosphite; 2-methyl-6-tert-butyl-4-(docosyloxycarbonylmethyl)phenyl 2,6-di-tert-pentylphenylfluorophosphite; tetrakis(difluorophosphite ester) of tetrakis(methylene3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate)methane;tetrakis(2,4-ii-tert-butylphenyl fluorophosphite ester) oftetrakis(methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane;tetrakis(2,4-di-terthexylphenyl fluorophosphite ester)oftetrakis(methylene 2-(3-tert-pentyl-4-hydroxyphenyl)acetate)methane tris(difluorophosphite ester) of trimethylolpropanetris3-(3,5-di-tert-butyl-4-hydroxy-phenyl)proponiate!,tris(3-methyl5-tert-butylphenyl fluorophosphite ester) of trimethylolethanetris 3-methyl-5-tert-butyl-4-hydroxybenzoate! and the like.

Sub-class IV (vii) A groups have the structure: ##STR13## wherein R⁵ andR⁶ are the same as before.

Typical organo fluorophosphorus compounds of formula IV having asub-class IV (vii) A group are:

tris(difluorophosphite ester) of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;tris(2,4-di-tert-butylphenyl fluorophosphite ester) of(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;tris(2,6-di-tert-butylphenyl fluorophosphite ester) of 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate; tris(methylfluorophosphite ester) of1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;tris(n-dodecyl fluorophosphite ester) oftris(4-hydroxybenzyl)isocyanurate and the like.

Sub-class IV (viii) A group have the structure: ##STR14## wherein R⁵ andR⁶ are as before.

Typical organo fluorophosphorus compounds of Formula IV having asub-class IV (viii) A groups are:

Difluorophosphite diester of alpha,alpha'-thiobis(2,6-di-tert-butyl-p-cresol); 2,4-di-tert-butylphenyl fluorophosphitediester of 4-hydroxybenzyl 3,5-di-tert-butyl-4-hydroxybenzyl sulfide;dodecyl fluorophosphite diester of bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; difluorophosphite diester ofbis-(3-methyl-5-tert-butyl-4-hydroxybenzyl)sulfide;2,6-di-tert-butylphenyl fluorophosphite diester ofbis-(3,5-didodecyl-4hydroxybenzyl)sulfide; phenyl fluorophosphitediester of bis-(3,5-di-isopropyl-4-hydroxybenzyl)sulfide and the like.

The preferred aromatic fluorophosphites of the present invention arebis(2,4-di-t-butylphenyl) fluorophosphite,2,2'-ethylidenebis(4,6-di-t-butylphenyl) fluorophosphite and2,2'-bis(2,6-di-tert-butylphenyl) fluorophosphite.

The aromatic fluorophosphites of the invention are particularly usefulas antioxidants. The antioxidants can be used in a broad range oforganic material normally subject to gradual degradation in the presenceof oxygen during use over an extended period. In other words, theorganic materials protected by the present antioxidants are of the typein which the art recognizes the need for antioxidant protection and towhich an antioxidant of some type is customarily added to obtain anextended service life The oxidative degradation protected against is thedeterioration of the organic composition during or after processingrather than, for example, combustion.

Examples of organic materials in which the antioxidants of thisinvention are useful include polymers, both homopolymers and copolymers,of olefinically unsaturated monomers, for example, polyolefins such aspolyethylene, polypropylene, polybutylene and the like.

Also, polyaalohydrocarbons such as polyvinyl chloride, polychloroprene,polyvinylidene chloride, polyfluoroolefins, and the like, are affordedstabilization. The antioxidants provide antioxidant protection innatural and synthetic rubbers such as copolymers of olefinicallyunsaturated monomers including styrene butadiene rubber (SBR rubber),ethylene-propylene copolymers, ethylene-propylene-diene terpolymers suchas the terpolymer of ethylene, propylene and cyclopentadiene or1,4-cyclooctadiene. Polybutadiene rubbers such as cis-polybutadienerubber are protected. Poly-2-chloro-1,3-butadiene (neoprene) andpoly-2-methyl-1,3-butadiene (isoprene rubber) are stabilized by thepresent additives. Likewise, acrylonitrile-butadiene-styrene (ABS)resins are effectively stabilized. Ethylene-vinyl acetate copolymers(EVA) are protected, as are butene-methylacrylate copolymers.Nitrogen-containing polymers such as polyurethanes, nitrile rubber, andlauryl acrylate-vinyl pyrrolidone copolymers are effectively stabilized.Adhesive compositions such as solutions of polychloroprene (neoprene) intoluene are protected. Polyphenylene ethers such aspoly-2,6-dimethyl-1,4-phenylene ethers either alone or in combinationwith blending agents such synthetic rubbers are protected by the presentinvention. Likewise polystyrene and rubber modified polystyrene (i.e.high impact polystyrene) are stabilized.

Petroleum oils such as solvent-refined, midcontinent lubricating oil andGulf Coast lubricating oils are effectively stabilized. In hydrocarbonlubricating oils, both mineral and synthetic, the present antioxidantsare effective when used in combination with a zinc dihydrocarbyldithiophosphate e.g. zinc dialkyl dithiophosphate or zinc dialkaryldithiophosphate.

Synthetic ester lubricants such as those used in turbines and turbojetengines are given a high degree of stabilization. Typical syntheticester lubricants include di-2-ethylhexyl sebacate, trimethylolpropanetripelargonate C₅₋₉ aliphatic monocarboxylic esters of pentaerythritol,complex esters formed by condensing under esterifying conditions,mixtures of polyols, polycarboxylic acids, and aliphatic monocarboxylicacids and/or monohydric alkanols. An example of these complex esters isthe condensation product formed from adipic acid, ethylene glycol and amixture of C₅₋₉ aliphatic monocarboxylic acids. Plasticizers such asdioctyl phthalate are effectively protected. Heavy petroleum fractionssuch as tar and asphalt can also be protected should the need arise.

Polyamides such as adipic acid-1,6-diaminohexane condensates andpoly-6-aminohexanoic acid (nylon) are effectively stabilized.Polyalkylene oxides such as copolymers of phenol with ethylene oxide orpropylene oxide are stabilized. Polyphenyl ethers such aspoly-2,6-dimethylphenyl ether formed by polymerization of2,6-dimethylphenyl using a copper-pyridine catalyst are stabilized.Polycarbonate plastics and polyformaldehydes are also protected.

Linear polyesters such as phthalic anhydride-glycol condensates, polyethylene terephthalate! (PET), and poly butylene terephthalate! (PBT),are given a high degree of protection. Other polyesters such astrimellitic acid-glycerol condensates are also protected. Polyacrylatessuch as polymethylacrylate and polymethylmethacrylate are effectivelystabilized. Polyacrylonitriles an copolymers of acrylonitriles withother olefinically unsaturated monomers such as methylmethacrylates arealso effectively stabilized.

The antioxidants of the present invention are preferably used in eitherthermoset or thermoplastic polymer compositions. The thermoset polymersare those plastics which when subjected to heat, will normally becomeinfusible or insoluble and as such cannot be remelted. They haveelaborately cross-linked three dimensional structures and are used forplastics, elastomers, coatings and adhesives.

In contrast to the thermoset polymers, most thermoplastic polymers canbe made to soften and take a new shape by the application of heat andpressure. Thermoplastic polymers comprise long-chain molecules oftenwithout any branching (e.g., high density polyethyene). Thermoplasticpolymers normally are rigid at operating temperatures, but can beremelted and reprocessed. They include polyethylene, polycarbonate,polypropylene, polystyrene, polyvinyl chloride,acrylonitrile-butadiene-styrene (ABS), nylon, and the like, includingpolymers intended for high temperature applications. The most preferredorganic compounds intended for the practice of the present invention arepolypropylene and polyethylene.

The more preferred utility of the new additives is in the stabilizationof thermoplastic polymers during processing such as during extrusion. Ofthese the most preferred polymers are polyethylene, polypropylene,linear low density polyethylene and polycarbonates.

The antioxidants of the present invention are useful to controloxidative and color degradation of resins used as tackifiers inadhesives. The resin which can be protected include synthetichydrocarbon resins, such as cycloaliphatic C₅ resins, aromatic C₉resins, terpene resins and the like. Also included are natural resins,such as wood rosin, gum rosin and toll oil rosin which are processed fortackifier applications.

The antioxidants are incorporated into the organic material in a smallbut effective amount so as to provide the required . .antioxdant.!..Iadd.antioxidant .Iaddend.protection. A useful range is generally fromabout 0.005 to about 5 weight percent of organic material, and apreferred range is from about 0.01 to 2 weight percent.

Methods of incorporating the antioxidants into the organic material arewell known. For example, if the material is

liquid, the additive can be merely mixed into the material. Solidorganic materials can be merely sprayed with a solution of the additivein a volatile solvent. For example, stabilized grain products resultfrom spraying the grain with a toluene solution of the antioxidant. Inthe case of rubbery polymers, the additive the final emulsion ofsolution polymerization mixture and then coagulating or removing solventto recover the stabilized polymer. It can also be added at thecompounding stage by merely mixing the additive with the rubbery polymerin commercial mixing equipment such as a Banbury blender. In thismanner, rubbery polymers such as styrene-butadiene rubber,cis-polybutadiene or isoprene polymers are blended with the antioxidanttogether with the other ingredients normally added such as carbon black,oil, sulfur, zinc oxide, stearic acid, vulcanization accelerators, andthe like. Following mastication, the resultant mixture is fabricated andmolded into a finished form and vulcanized.

The fluorophosphites of the present invention are readily made byreacting the appropriate phenolic compound with phosphorus ..trichlorideoor phosphorus tribromide.!. .Iadd.trichlorideor .Iaddend.toform an aryloxy mono- or di-halo (e.g., Cl . .or Br.!.) phosphite. Thisin turn is reacted with a fluorinated compound such as HF, LiF, NaF, KF,RbF, CsF, SbF₃, SbF₅, AgF, HgF₂, CoF₃,SF₄ and the like which exchange Ffor C₁ . .or Br.!. bonded to phosphorus.

In making compounds of Formula I-IV, a phenol is reacted with PCl₃ . .orPBr₃ .!. to form a chloro . .or bromo-.!. phosphite intermediate whichis then reacted with a fluorinating agent as shown in the followingequations. ##STR15##

In the above illustration, PCl₃ is used . .but PBr₃ could also beused.!.. Likewise, KF is used as the fluorinating agent but any of theother fluorinating agents could be used in its place.

The amount of PCl₃ . .or PBr₃ .!. used to form the intermediate chloro ..or bromo.!.phosphite depends on the number of hydroxyl groups in thephenolic reactant and the average number of residual P-Cl . .or P-Br.!.groups desired in the intermediate. For example, if one mole of PCl₃ isreacted with one mole of a monohydroxy phenolic compound the averageintermediate will be a dichlorophosphite. Likewise if two moles of amonohydroxy phenolic compound are reacted with one mole of PCl₃ theaverage intermediate compound will be a monochlorophosphite. When onemole of an ortho-ortho bridged diphenol is reacted with one mole ofPCl₃, the major component in the intermediate will be a cyclicmonochlorophosphite such as may be used to make a fluorophosphite ofFormula II.

The starting phenolic compounds are well known and described in theliterature such as in U.S. Pat. No. 2,836,577; U. S. Pat. No. 944,986;U.S. Pat. No. 3,562,338; U.S. Pat. No. 1,972,599; U.S. Pat. No.2,807,653; U.S. Pat. No. 3,4494441; U.S. 1,892,990; U.S. Pat. No.2,394,754; U. S. 2,479,948; U.S. Pat. No. 2,905,674; U.S. Pat. No.3,367,980; U.S. Pat. No. 3,069,384; U.S. Pat. No. 2,202,877; U.S. Pat.No. 2,313,782; U.S. Pat. No. 3,065,275; U.S. Pat. No. 2,84,619; U.S.Pat. No. 2,315,556; U.S. Pat. No. 2,469,469; U.S. Pat. No. 2,836,609;U.S. Pat. No. 3,146,273; U.S. Pat. No. 2,008,032; U.S. Pat. No.2,714,120; U.S. Pat. No. 3,093,587; U.S. Pat. No. 3,0601121; U.S.2,538,355; U.S. Pat. No. 2,364,338; U.S. Pat. No. 3,330,859; U.S. Pat.No. 3,062,896; U.S. Pat. No. 3,026,64; U.S. Pat. No. 3,531,483; J. A.Chem. Soc. 78 1069 (1956) and others.

The reaction of the PCl₃ or PBr₃ with the phenol is preferably conductedin an aprotic solvent such as THF, benzene, toluene, xylene, heptane,octane, cyclohexane and the like. The reaction can also be conducted inan excess of PCl₃ or PBr₃ which functions as a solvent or reactionmedium. The reaction temperature should be high enough to cause thereaction to proceed at a reasonable rae but not so high as to causedecomposition. A useful temperature range is from -30° to 300° C. Apreferred temperature range is 0-100° C. and a more referred temperaturerange is about 25-75° C. and must preferably at reflux temperature.

The chloro or bromophosphite intermediate is fluorinated by reactionwith at least an equivalent amount of the fluorinating agent based ..o.!. .Iadd.on .Iaddend.the equivalent of Cl . .and/or Br.!. bound tophosphorus. An excess can be used. The fluorination is preferablyconducted in a aprotic solvent. The reaction can be conducted in thesame reaction mixture resulting from the preparation of theintermediate.

The fluorination temperature should be high enough to cause the fluorineto replace the chlorine or bromine but not so high as to causedecomposition. A useful temperature range is about 10-300° C., morepreferably 20-150° C. and most preferably at reflux.

The aromatic fluorophosphites of the present invention may be used aloneas the antioxidant or may be used in combination with phenolicantioxidants, thioesters such as dilauryl thiodipropionate and distearylthiodipropionate, light stabilizers such as hindered amines orultraviolet light absorbers, metal deactivators, pigments, dyes,lubricants such as calcium stearate, nucleation agents and talc andother fillers.

Some representative examples of useful UV stabilizers are:

    ______________________________________    UV Stabilizers    ______________________________________    Nickel dibutyldithiocarbamate    2-hydroxy-4-n-octyloxybenzophenone    2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydrozybenzoate    Nickel bis o-ethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate    2-(3',5'-di-tert-butyl-2'-hydroxyphenyl-5-chlorobenzotriazole    Bis(2,2,6,6-tetramethyl-piperridinyl-4)sebacate    Bis(1,2,2,6,6-pentamethyl-piperridinyl-4)sebacate    n-Butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-bis(1,2,2,6,6-pentamethyl-4-    piperridinyl)malonate    Dimethyl succinate polymer with 2,2,6,6-tetramethyl-1-piperridineethanol    N,N'-bis(2,2,6,6-tetramethyl-4-piperridinyl)-1,6-hexane diamine, polymer    with 2,4,6-trichloro-1,3,5-triazine and 2,4,4-trimethyl-1,2-pentanamine    polymeric hindered amines such as Gasorb UV3346 (American    Cyanamid): Spinuvex A-36 (Montedison); Chimassorb 944 (Ciba-Geigy)    2-(2'-hydroxy-3', 5'-di-tert-amylphenyl)benztriazole    2,2'-thiobis(4-tert-octylphenolato)butylamino-Nickel(II)    Nickel bis((ethyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-phosphate)    and the like.    ______________________________________

Phenolic antioxidants which are suitable for use in the presentinvention are well known in the art and include2,6-di-t-butyl-4-methylphenol; 2,6-di-t-butyl-4-methoxymethylphenol;2,6-dioctadecyl-4-methylphenol; 3,5-di-t-butyl-4-hydroxyanisole;2,5-di-t-butyl-4-hydroxyanisole; 4-(hydroxymethyl)-2,6-di-t-butylphenol;4,4'-methylenebis(2,6-di-t-butylphenol);2,2'-ethylidenebis(4,6-di-t-butylphenol);4,4'-thiobis(2-methyl-6-t-butylphenol); tetrakis(methylene3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate)methane:1,3,5-tris(3,5-di-t-butyl-4-hydroxybentyl)isocyanurate:0,0,-di-n-octadecy((3,5-di-t-butyl-4-hydroxybenzyl)phosphonate;octadecyl 3-(3,5-dit-butyl-4-hydroxyphenyl)propionate;2,2'-oxamidobisethyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate;calcium bis(0-ethyl(3,5-di-t-butyl-4-hydroxybenzyl)phosphonate) andmixtures thereof. A particularly preferred phenolic antioxidant is1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4hydroxybenzyl)benzene whichis available from Ethyl Corporation as 10 Ethanox® 330 Atioxidant.

When utilized, the phenolic antioxidants are preferably present with thearomatic fluorophosphites in an amount in the range of from about 0.005to about 3.0 percent by weight based on the weight of the totalcomposition.

The following examples are presented to illustrate certain specificembodiments of the invention, but are not intended to be construed so asto be restrictive of the spirit and scope thereof.

EXAMPLE 1 Preparation of . .bis(2,6di-t-butylphenvl).!. .Iadd.bis(2,6-di-t-butylphenyl) .Iaddend.fluorophosphite

Under an atmosphere of nitrogen, 10.1 grams of bis(2,6-di-t-butylphenyl)chlorophosphite, 2.4 grams of anhydrous potassium fluoride and 100 ml ofanhydrous tetrahydrofuran were combined and heated to reflux for 17hours. Next, and additional 1.0 grams of anhydrous potassium fluoridewas added to the mixture. The mixture was heated at reflux for a totalof 44 hours and allowed to cool. The resulting slurry was filtered andthe filtrate was concentrated under vacuum. The crude product wasdissolved in n-heptane and filtered through basic alumina, eluting withn-heptane. The early fractions containing the least polar product wereconcentrated to 3.6 grams of pale oil. The oil was purified bychromatography on basic alumina, eluting with n-heptane, to yield 1.8grams of clear oil which solidified to a white solid upon standing.

Spectral analysis (H-NMR, P-NMR, F-NM, mass spectrometry (MS)) confirmedthe identity of the which solid as bis(2,6-di-t-butylphenyl)fluorophosphite.

EXAMPLE 2

Preparation of bis(2,6-di-t-butyl-4-(2-carbooctadecyloxyethyl)phenyl)flurophosphite

Under a nitrogen atmosphere, 20 grams ofbis(2,6-di-t-butyl-4-(2-carbooctadecyloxyethyl)phenyl chlorophosphite(75 weight percent purity), 3.0 grams of potassium fluoride, and 100 mlof anhydrous tetrahydrofuran were combined and heated to refluxtemperature. After heating the mixture for 40 hours at refluxtemperature, the mixture was allowed to cool and was subsequentlyfiltered. The filtrate was concentrated to 19.4 grams of white solids.By quantitative P-NMR, the conversion was about 90% and the yield was86% of bis(2,6-di-t-butyl-4-(2-carbooctadecyloxyethyl)phenylfluorophosphite.

A sample of the crude product was purified by chromatography foranalysis and polymer testing. The spectral analysis (H-NMR, P-NMR andF-NMR) confirmed the identity of the product asbis(2,6-di-t-butyl-4-(2-carbooctadecyloxyethyl)phenyl fluorophosphite.

EXAMPLE 3 Preparation of 2,2'-ethylidenebis(4,6-di-t-butylphenyl)fluorophosphite

Under a nitrogen atmosphere, 117 ml of phosphorus trichloride and 1.3 lof toluene were combined and the admixture was cooled to 5.C. A solutionof 573 grams of 2,2'-ethylidenebis(4,6-di-t-butylphenol), 375 ml oftriethylamine, and 2.01 of toluene was added dropwise to the admixtureover a period of 6 hours. The reaction mixture was maintained below atemperature of 10° C. during the addition. Next, the reaction mixturewas allowed to warm to ambient temperature. After 1 hour at ambienttemperature, 135 grams of antimony trifluoride was added to the mixtureto form a slurry. Next, the slurry was warmed to 85.C over a period of 1hour and maintained at this temperature for 4 hours. The crude reactionproduct comprised a pale green organic layer over a thick green oil. Thepale green organic layer was dacanted from the oil. The organic layerwas filtered through 165 grams of silica gel 60. The filter cake wasthen washed with toluene. The clear colorless filtrates wereconcentrated under vacuum to 617 grams of white solids. By quantitativeP-NMR, the solids were determined to be a 4:1 mixture of the twopossible diasteriomers of 2,2'-ethylidenebis(4,6-di-t-butylphenyl)fluorophosphite. An analysis by H-NMR, P-NMR, F-NMR and MS wasconsistent with these structures.

EXAMPLE 4

Preparation of . .bis(2,4-di-t-butylohenyl).!. .Iadd.bis(2,4-di-t-butylphenyl) .Iaddend.fluorophosphite

Under a nitrogen atmosphere, 6 ml of phosphorus trichloride and 100 mlof anhydrous tetrahydrofuran were combined and the admixture was cooledbelow 10.C. A solution of 28.7 grams of 2,4-di-t-butylphenol, 20 ml oftriethylamine, and 150 ml of anhydrous tetrahydrofuran was addeddropwise to the admixture over a period of 80 minutes. The resultingslurry was allowed to warm to ambient temperature. After 2 hours atambient temperature, 8 grams of antimony trifluoride was added to theslurry. The slurry was then heated to reflux temperature and maintainedat this temperature for 1 hour. The slurry was allowed to cool and thenfiltered through basic aluminum oxide. The filter cake was washed withtoluene. The filtrates were concentrated under vacuum to 30.8 grams of apale yellow oil. A 27 gram portion of the crude product was dissolved in150 ml of n-heptane and filtered to remove insoluble materials. Thefiltrate was concentrated to 25 grams of a pale yellow oil. The oil wasnext stirred with 100 ml of acetonitrile. The white solid which wasformed was collected by filtration to yield 17.5 grams ofbis(2,4-di-t-butylphenyl) fluorophosphite. The H-NMR, P-NMR, F-NMR andMS of the solid were consistent with this structure.

EXAMPLE 5 Preparation of 4,4'-methylenebis(3,5-di-tert-butylphenyl)tetrafluorodiphosphite.

In a reaction vessel under nitrogen was placed 10.7 grams of4,4'-methylenebis(2,6-di-tert-butylphenol), 4.4 ml of PCl₃, 7 ml oftriethylamine and 100 ml of toluene. The mixture was heated at 50° C.with stirring for 5.5 hours. It was then heated to 80° C. and held at80° C. for 36 hours. Then 7.2 grams of SbF₃ was added and the mixturestirred 4.5 hours at 80° C. and then cooled. Two phases forced. Theupper yellow liquid phase was decanted and filtered through silica geland the filtrate was evaporated to give 11.4 grams residue whichsolidified to a yellow waxy solid. The crude product was recrystallizedfrom acetonitrile to obtain a white solid (mp. 125-126° C.). The H-NMR,p-NMR were consistent With the target tetrafluorodiphosphite.

EXAMPLE 6 Preparation of 2,2-bis(4,6-di-tert-butylphenyl)fluorophosphite

Under a nitrogen atmosphere a solution of 8.2 grams of4,4',6,6,-tetra-tert-butyl-2,2'biphenyl and 5.9 ml of triethylamine in25 ml of toluene was added to a cooled (5° C.) solution of 1.8 ml ofPCl₃ in 20 ml of toluene over a 1.25 hour period. At the end of theaddition, the slurry was stirred 15 minutes and the mixture then warmedto ambient temperature. After stirring overnight, 2.0 grams of SbF₃ wasadded. The resulting slurry was heated to and maintained at 85° C. for6.5 hours. After cooling, the toluene layer was decanted from the blacksolid residue and filtered through Celite. The filtrate was evaporatedto give about 9 grams of a yellow oil. The yellow oil was washed withacetonitrile and purified by column chromatography in a n-heptanesolvent. The product recovered from the eluant was a white solid with am.p. of 188° C. The P-NMR showed a 1300 Hz doublet at 132.4 ppm (from H₃PO₄, CDCl₃) which confirmed the identify of the product a the targetcompound.

    ______________________________________    Code for Aromatic Fluorphosphites Used in Example 7-9    Chemical    Code   Description    ______________________________________    P-1    bis(2,6-di-t-butylphenyl)fluorophosphite    P-2    bis(2,4-di-t-butylphenyl)fluorophosphite    P-3    2,2'-ethylidenebis(4,6-di-t-butylphenyl)fluorophosphite    P-4    bis(2,6-di-t-butyl-4-(2-carbooctadecyloxyethyl)phenyl)fluoro-           phosphite    ______________________________________

EXAMPLE 7

In order to demonstrate the effectiveness of the aromaticfluorophosphite of the present invention as processing stabilizers,bis(2,6-di-t-butyl-4-(2-carbooctadecyloxyethyl)phenyl) fluorophosphite(P-4) and1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene(Ethanox® 330 Antioxidant) were incorporated into polypropylene powderin accordance with the following procedure. The P-4 and Ethanox® 330Antioxidant were dissolved in a small amount of methylene chloride andmixed with 50 grams of polypropylene powder (Profax® 6501 polypropylenefrom Hercules). The mixture was then dry blended with 450g ofpolypropylene in a nitrogen atmosphere. In some of the formulations,1000 ppm of calcium stearate (Mallinckrodt RSN 248D) was utilized as anacid neutralizer and lubricating agent. The blended material wasextruded under nitrogen on a twin screw mixer (Brabender, 30 rpm) withthe temperature profile: zone one 150° C., zone two and zone three--245°C. Then, multiple extrusions were run on the pellets on a single screwextruder (Brabender L/D 24:1) at 550° F. The stock temperature was 265°C. and the screw speed was 30 rpm in an air atmosphere. The extrudedstrand was cooled by passing it through a room temperature (24-29° C.)water bath. Water carryover was minimized by an air knife that blew theexcess water from the strand before it entered the pelletizer. The meltflow index (MFI) was determined with a Tinium Olsen ExtrusionPlastometer according to ASTM Method D-1238 Condition L (230° C.-2160 gload). Using the same samples, a 60 mil sheet was pressed out at 375° F.and the color was determined with a Hunterlab Optical Sensor Model D25.

The results of these tests are shown in Table I.

                  TABLE I    ______________________________________                           Melt Flow Index                                      Yellowness Index                           Extrusion  Extrusion    Test            Wt.    Pass No.   Pass No.    No.   Antioxidant                    %      1    2    3    1    2    3    ______________________________________    1     None             13.8 26.9 --   5.0  6.2  --    2     Ethanox 330                    0.05   6.7  9.4  12.6 7.2  --   9.6    3     P-4       0.05   6.7  9.2  12.6 5.6  --   7.9          Ethanox 330                    0.05    4     Ethanox 330                    0.05   8.9  13.2 18.8 4.5  --   6.1          calcium          stearate  0.10    5     Ethanox 330                    0.05   7.9  11.5 16.2 4.5  --   6.5          P-4       0.05          calcium          stearate  0.10    ______________________________________

These results of these tests show P-4 was effective in suppressing colorwhen used with Ethanox® 330 Antioxidant and reducing the degradation ofpolypropylene when used with Ethanox® 330 Antioxidant and calciumstearate.

EXAMPLE 8

A series of tests was performed in the same manner as Example 7 tomeasure Melt Flow Index except that aromatic fluorophosphites,designated as P-2 and P-3, and a different batch of Profax 6501polypropylene were utilized. In addition, calcium stearate and Ethanox®330 Antioxidant were used in all tests.

The results of these tests are shown in Table II.

                  TABLE II    ______________________________________                         Melt Flow Index                         Extrusion Pass No.    Test No. Antioxidant Wt. %     1     3    5    ______________________________________    1        Ethanox 330 0.05      8    18    --             Calcium stearate                         0.10    2        P-2         0.050     5.4  9.5   15.4             Ethanox 330 0.050             Calcium stearate                         0.100    3        P-3         0.050     5.5  9.3   15.1             Ethanox 330 0.050             Calcium stearate                         0.100    ______________________________________

The results of these tests demonstrate that the P-2 and P-'aromaticfluorophosphites were effective in reducing the degradation ofpolypropylene.

EXAMPLE . .2.!. .Iadd.9.Iaddend.

A series of tests were performed in the same manner as Example 8 exceptthat an aromatic fluorophosphite, designated P-1, and a different batchof Profax 6501 polypropylene were utilized and, the multiple extrusionswere run at 500° F.

The results of these tests are shown in Table III.

                  TABLE III    ______________________________________                         Melt Flow Index                         Extrusion Pass No.    Test No. Antioxidant Wt. %     1     3    5    ______________________________________    1        Ethanox 330 0.05      3.4  6.2   9.6             Calcium stearate                         0.10    2        Ethanox 330 0.05      2.4  3.8   5.5             Calcium stearate                         0.10             P-1         0.05    ______________________________________

The results of these tests demonstrate that P-1 aromatic fluorophosphitewas effective in reducing the degradation of polypropylene.

EXAMPLE 10

The hydrolytic stabilities of the fluorophosphites listed weredetermined by dissolving 100 mg of the fluorophosphite in a mixture of 2ml of tetrahydrofuran, 0.2 ml of water and 0.3 ml of d⁸ -tetrahydrofuran(deuteraed THF). The mixtures were stirred at 76° F. and were monitoredby P-NMR.

The results of these tests are set forth in Table IV.

                  TABLE IV    ______________________________________    SAMPLE     % HYDROLYSIS AFTER 2 WEEKS    ______________________________________    P-1        0    P-2        0    P-3        <1    ______________________________________

The results of these tests show the resistance of the fluorophosphitesto hydrolysis over extended periods of time, i.e., 2 weeks.

The invention is not limited to the above-described specific embodimentsthereof; it must be understood, therefore, that the detail involved inthe descriptions of the specific embodiments is presented for thepurpose of illustration only, and that reasonable variations, which willbe apparent to those skilled in the art, can be made in tis inventionwithout departing from the spirit and scope thereof.

What is claimed:
 1. An aromatic fluorophosphorus compound suitable foruse as an antioxidant said compound being selected from fluorophosphoruscompounds having the structure:

    . .(RO--) P (--F).sub.2                                    Formula V

wherein R is an substituted aryl group wherein the substituents aretert-alkyl groups:

    (R'O--).sub.2 P-F                                          Fomula VI

wherein R'is a substituted aryl group wherein the substituents areselected from sec-alkyl, tert-alkyl, aralkyl, cycloalkyl, hydroxy,alkoxy, aryloxy, halo, acyloxy, and alkoxy carbonylalkyl:.!. ##STR16##wherein R¹ and R² are substituted or unsubstituted . .aryl.!..Iadd.phenyl .Iaddend.groups wherein the . .substituent.!..Iadd.substituents .Iaddend.are selected from alkyl, aryl, aralkyl,cycloalkyl, . .hydroxy,.!. alkoxy, aryloxy, and halo. .:.!..Iadd.,.Iaddend.and X is selected from the group consisting of a single bondconnecting R¹ and R² and divalent bridging groups selected from divalentaliphatic hydrocarbon groups containing 1-12 carbon atoms, --O-- and--S_(q) -- wherein q is an integer from 1 to
 3. .:.!..Iadd., and whereinaryl is selected from the group consisting of phenyl, o-tolyl, p-tolyl,naphthyl, 4-phenylphenyl and 4-sec-hexylphenyl..Iaddend.. . ##STR17##wherein R is a substituted or unsubstituted aryl group wherein thesubstituents are selected from alkyl, aryl, aralkyl, cycloalkyl,hydroxy, alkoxy, aryloxy, halo, alkoxycarbonyl, alkoxycarbonyl-alkyl andacyloxy, and R³ is selected from the group consisting of alkyl,cycloalkyl, aralkyl, aryl, substituted aryl, alkoxy, cycloalkoxy andaralkoxy; and ##STR18## wherein A is a mono- or poly-nuclear aromaticgroup, R⁴ is independently selected from fluorine, aryloxy,alkylaryloxy, alkoxy and polyalkoxy, r is an integer from 1 to 4, s isan integer from 0 to 3 and (r + s) equals the valence of A..!.. .
 2. Acompound of claim 1 namely bis(2,6-di-tertbutylphenyl)fluorophosphite..!.. .3. A compound of claim 1 namely:bis(2,4-di-tert-butylphenyl) fluorophosphite..!.. .4. A compound ofclaim 1 namely bis(4-octadecyloxycarbonylethyl-2,6-di-tert-butylphenyl)fluorophosphite..!.5. A compound of claim 1 namely:2,2'ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite. . .6. Acompound of claim 1 namely: bis(difluorophosphite ester) of4,4'-methylenebis(2,6-di-tert-butylphenol)..!.7. A compound of claim 1namely: 2,2'-bis(4,6-di-tert-butylphenyl) fluorophosphite.
 8. . .Organicmaterial.!. .Iadd.A polymer of an olefinically unsaturated monomer.Iaddend.normally susceptible to gradual oxidative degradation when incontact with oxygen, . .said organic material containing.!. .Iadd.andhaving incorporated therein by mixing or spraying .Iaddend.anantioxidant amount of an aromatic fluorophosphorus compound, saidcompound being characterized by having at least one benzene group bondedthrough oxygen to a trivalent phosphorus atom and at least one fluorineatom bonded to said phosphorus atom.
 9. An organic composition of claim8 wherein said fluorophosphorus compound is selected from the groupconsisting of compounds having the structures;

    (RO--).sub.n P (--F).sub.3--n                              Formula I

wherein R is a substituted or unsubstituted . .aryl.!. .Iadd.phenyl.Iaddend.group wherein the substituents are selected from alkyl, aryl,aralkyl, cycloalkyl, . .hydroxy,.!. alkoxy, aryloxy, halo,alkoxycarbonyl, alkoxycarbonylalkyl and acyloxy and n is 1 or 2,.Iadd.and wherein aryl is selected from the group consisting of phenyl,o-tolyl, p-tolyl, naphthyl, 4-phenylphenyl and4-sec-hexylphenyl;.Iaddend. ##STR19## wherein R¹ and R² are substitutedor unsubstituted . .aryl.!. .Iadd.phenyl .Iaddend.groups wherein thesubstituents are selected from alkyl, aryl, aralkyl, cycloalkyl, ..hydroxy,.!. alkoxy, aryloxy and halo, and X is selected . .rom.!..Iadd.from .Iaddend.the group consisting of a single bond connecting R¹and R² and divalent bridging groups selected from divalent aliphatichydrocarbons containing 1-12 carbon atoms, --O-- and --S_(q--) wherein qis an integer from 1 to
 3. .;.!..Iadd., and wherein aryl is selectedfrom the group consisting of pheynl, o-tolyl, p-tolyl, naphthyl,4-phenylphenyl and 4-sec-hexylphenyl; and .Iaddend. ##STR20## wherein Ris as previously defined for Formula I and . .R₃ .!. .Iadd.R³.Iaddend.is selected from the group consisting of alkl, cycloalkyl,aralkyl, aryl, substituted aryl, alkoxy, cycloalkoxy, aryloxy andaralkoxy. .; and.!..Iadd., and wherein aryl is selected from the groupconsisting of phenyl, o-tolyl, p-tolyl, naphthyl, 4-phenylphenyl and4-sec-hexylphenyl .Iaddend. ##STR21##? wherein A is a mono orpolynuclear aromatic group, R⁴ is independently selected from fluorine,aryloxy, alkaryloxy, alkoxy and polyalkoxy and r is an integer from 1 to4, s is an integer from 0 to 3 and (r+s) equals the valence of A.!.. ..10. A composition of claim 8 wherein said organic material is a polymerof an olefinically unsaturated monomer..!.11. A composition of claim ..9.!. .Iadd.44 .Iaddend.wherein said organic material is a polymer of anolefinically unsaturated monomer.
 2. A composition of claim . .11.!..Iadd.9 .Iaddend.wherein said compound has Formula I.Iadd., and R is asubstituted phenyl group.Iaddend..
 13. A composition of claim 12 whereinn is 2 and said substituents are selected from alkyls having 1-20 carbonatoms, . .aryls having 6-12 carbon atoms.!. .Iadd.phenyl, o-tolyl,p-tolyl, naphthyl, 4-phenylphenyl, 4-sec-hexylphenyl.Iaddend., aralkylshaving 7-12 carbon atoms, cycloalkyls having 5-8 carbon atoms, ..hydroxy,.!. alkoxy having 1-12 carbon atoms, aryloxy having 6-12 carbonatoms, halo, . .alkoxycarbonylalkyl having 1-20 carbon atoms in itsalkoxy moiety and 1-3 carbon atoms in its alkyl moiety, alkoxycarbonylhaving 1--20 carbon atoms in its alkoxy moiety.!. and acyloxy having 1-4carbon atoms.
 14. A composition of claim 13 wherein said substituentsare selected from alkyl having 1-20 carbon atoms . .and alkoxycarbonylalkyl having 1-20 carbon atoms in its alkoxy moiety and 4 1-3carbon atoms in its alkyl moiety.!..
 15. A composition of claim 14wherein said fluorophosphite compound is bis(2,6-di-tert-butylphenyl)fluorophosphite.
 16. A composition or claim 14 wherein saidfluorophosphite is bis(2,4-di-tert-butylphenyl) fluorophosphite.
 17. Acomposition of claim . .14.!. .Iadd.12 .Iaddend.wherein saidfluorophosphite compound isbis(4-octadecyloxycarbonylethyl-2,6-di-tert-butylphenyl)fluorophosphite.
 8. A composition of claim 12 wherein n is
 1. 19. Acomposition of claim 9 wherein said fluorophosphite compound has FormulaII wherein said substituents are selected from alkyl having 1-20 carbonatoms, . .aryl having 6-12 carbon atoms.!. .Iadd.phenyl, o-tolyl,p-tolyl, naphthyl, 4-phenylphenyl, 4-sec-hexylphenyl.Iaddend., aralkylhaving 7-12 carbon atoms, cycloalkyl having 5-8 carbon atoms, ..hydroxy,.!. alkoxy having 1-12 carbon . .toms.!. .Iadd.atoms.Iaddend.,aryloxy having 6-12 carbon atoms and halo, and X is selected from thegroup consisting of a single bond connecting R¹ and R² and divalentbridging groups selected from divalent aliphatic hydrocarbon groupscontaining 1-12 carbon atoms, --O-- and --S_(q) -- wherein q is aninteger from 1-3.
 20. A composition of claim 19 wherein said substituentgroups are alkyls containing 1-20 carbon atoms.
 21. A composition ofclaim 20 wherein said fluorophosphorus compound is2,2'-ethylidenebis(4,6-di-tert-butylphenyl) fluorophosphite. . Acomposition of claim 20 wherein said fluorophosphorus compound is2,2'-methylenebis (4-methyl-6-tert-butylphenyl) fluorophosphite.
 23. Acomposition of claim 20 wherein said fluorophosphite compound is..22,2,.!. .Iadd.2,2'.Iaddend.-bis(4,6-di-tert-butylphenyl)fluorophosphite.
 24. A composition of claim 9 wherein saidfluorophosphorus compound has Formula III wherein said substituents areselected from alkyls having 1-20 carbon atoms, . .aryls having 6-12carbon atoms.!. .Iadd.phenyl, o-tolyl, p-tolyl, naphthyl,4-phenylphenyl, 4-sec-hexylphenyl.Iaddend., aralkyls having 7-12 carbonatoms, cycloalkyls having 5-8 carbon atoms, . .hydroxy,.!. alkoxy having1-12 carbon atoms, aryloxy having 6-12 carbon atoms, halo,alkoxycarbonylalkyl having 1-20 carbon atoms in its alkoxy moiety and1-3 carbon atoms in its alkyl moiety, alkoxycarbonyl having 1-20 carbonatoms in its alkoxy moiety and acyloxy having 1-4 carbon atoms, and R³is selected from alkyl having 1-20 carbon atoms, cycloakyl having 5-8carbon atoms and aralkyls having 7-12 carbon atoms which are bondedthrough . .oxyqen.!. .Iadd.oxygen .Iaddend.to phosphorus and arylshaving 6-12 carbon atoms, alkyl having 1-20 carbon atoms, cycloalkylshaving 5-8 carbon atoms and aralkyls having 7-12 carbon atoms which arebonded directly to said phosphorus. . .25. A composition of claim 9wherein said fluorophosphorus compound has Formula IV..!.. .26. Acomposition of claim 25 wherein A has a structure selected from:##STR22## wherein R⁵ and R⁶ are hydrogen or alkyl having 1-12 carbonatoms, y is an integer from 2 to 3, x is an integer from 1 to 3, t is aninteger from 2 to 3, u is an integer from 0 to 4, (t+u) equals 2 to 6, wis an integer from 1 to 4, R⁷ is hydrogen or an alkyl having 1 to 6carbon atoms, R⁸ is an aliphatic hydrocarbon radical having 1-30 carbonatoms and having valence w, v is an integer from 0 to 4, R⁹ is analiphatic hydrocarbon radical having 1 to 6 carbon atoms and havingvalence y..!.. .27. A composition of claim 26 wherein saidfluorophosphorus compound is 2,5-di-tert-butyl-1,4-phenylene bis(difluorophosphite)..!.. .28. A composition of claim 26 wherein saidfluorophosphorus compound is 4,4'-methylenebis(2,6-di-tert-butylphenyl)bis(difluorophosphite)..!.. .29. A composition of claim 26 wherein saidfluorophosphite compound is the tris(difluorophosphite ester) of1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene..!.. .30. A composition of claim 26 wherein saidfluorophosphorus compound is the tetrakis(difluorophosphite ester) oftetrakis(methylene 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate)methane..!.. .31. A composition of claim 26 wherein saidfluorophosphite compound is difluorophosphite ester of octadecyl3-(3,5-di-tert-butylhydroxyphenyl)propioniate..!.32. An organiccomposition of claim 8 further characterized by containing about 0.005-5wt. percent of a phenolic antioxidant.
 33. An organic composition ofclaim 9 further characterized by containing about 0.005-5 wt. percent ofa phenolic antioxidant.
 34. An organic composition of claim 12 furthercharacterized by containing about 0.005-5 wt. percent of a phenolicantioxidant.
 35. An organic composition of claim 15 furthercharacterized by containing about 0.005-5 wt. percent of a phenolicantioxidant.
 36. An organic composition of claim 16 furthercharacterized by containing about 0.005-5 wt. percent of a phenolicantioxidant.
 37. An organic composition of claim 17 furthercharacterized by containing about 0.005-5 wt. percent of a phenolicantioxidant.
 38. An organic composition of claim 19 furthercharacterized by containing about 0.005-5 wt. percent of a phenolicantioxidant.
 39. An organic composition of claim 21 furthercharacterized by containing about 0.005-5 wt. percent of a phenolicantioxidant.
 40. An organic composition of claim 39 wherein saidphenolic antioxidant is 1,3,5-tris(3,5-di-tert-butyl-. .b.!.4-hydroxybenzyl)-2,4,6-trimethylbenzene. . .41. An organic compositionof claim 39 further characterized by containing about 0.005-5 wt.percent of a phenolic antioxidant..!.. .42. An organic composition ofclaim 25 further characterized by containing about 0.005-5 wt. percentof a phenolic antioxidant..!..Iadd.43. A aromatic fluorophosphoruscompound suitable for use as an antioxidant, said compound beingselected from the group consisting of bis(2,4-di-tert-butylphenyl)fluorophosphite;bis(4-octadecyloxycarbonylethyl-2,6-di-tert-butylphenyl)fluorophosphite; and4,4'-methylenebis(2,6-di-tert-butylphenyl)bis(difluorosphite)..Iaddend..Iadd.44.A compound of claim 1 combined in an antioxidant amount with an organicmaterial normally susceptible to gradual oxidative degradation when incontact with oxygen..Iaddend.